Kinetics of the OH + HCNO Reaction

Abstract

The kinetics of the OH + HCNO reaction was studied. The total rate constant was measured by LIF detection of OH using two different OH precursors, both of which gave identical results. We obtain k = (2.69 +/- 0.41) x 10(-12) exp[(750.2 +/- 49.8)/T] cm(3) molecule(-1) s(-1) over the temperature range 298-386 K, with a value of k = (3.39 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1) at 296 K. CO, H(2)CO, NO, and HNO products were detected using infrared laser absorption spectroscopy. On the basis of these measurements, we conclude that CO + H(2)NO and HNO + HCO are the major product channels, with a minor contribution from H(2)CO + NO.

Product Channels of the CN + HCNO Reaction

“…No experimental data has previously been reported for these reactions. We obtained upper limits for the 298 K rate constants of reactions 10−13 using standard pseudofirst order kinetics techniques, similar to our previous reports of the kinetics of HCNO with OH, 11 CN, 12 and NCO 13 radicals. For the NH + HCNO reaction, we used laser induced fluorescence (LIF) at 336 nm to monitor the decay of NH radicals produced by 266 nm Nd:YAG laser photolysis of HN 3 precursor molecules.…”

Kinetics of the NCO + HCNO Reaction

“…We can further deduce the products in 7b are also produced in very small amounts at most, because if OH were produced, it would react with HCNO to produce a significant yield of CO molecules. 2 These observations would tend to point to 7a as the major product. FTIR spectra of HCNO and HCNO/SO 2 mixtures before and after photolysis, however, showed no obvious differences that can be attributed to HCN formation via 7a.…”

“…In our laboratory, we have previously studied the kinetics of the OH + HCNO and CN + HCNO reactions. 2,3 In this paper, we present a study of the kinetics of the reaction HCNO with the NCO radical. NCO is an important intermediate in several combustion environments, including the RAPRENO x process for reducing NO x emissions.…”

Theoretical studies and topological analysis of the electron density of clusters of O3 with HNCO and HCNO

“…Several experimental and computational studies on the kinetics of HCNO have been reported [16][17][18][19][20][21][22][23]. Despite the potential importance of O 3 , HNCO and HCNO we could not find neither experimental nor theoretical report on O 3 -HNCO or O 3 -HCNO interactions.…”